Recording blank



Augf 9, 1966 l. P. ECHEAGARAY 3,265,524

RECORDING BLANK Filed June 24, 1965 C l n f3 n u IN VEN TOR. [6N/1cm PECHEAGAM Y Afro/ways United States Patent O 3,265,524 RECORDING BLANKIgnacio P. Echeagaray, 4349 W. 132nd St., Cleveland, Ohio 44135 FiledJune 24, 1965, Ser. No. 470,318 8 Claims. (Cl. 117-36.8)

The present application is a continuation-in-part of application SerialNo. 257,208, field Feb. 8, 1963, now abandoned, which application was acontinuation-in-part of application Serial No. 112,300, tiled vMay 24,1961, and now abandoned.

The present invention relates to recording blanks and, moreparticularly, to a heat sensitive recording blank which may be marked bya heating stylus.

An object of the present invention is the provision of a new andimproved heat sensitive recording blank comprising a base materialhaving a heat sensitive coating including polyvinylidene chloride, whichcoating is engageable with a heating stylus and upon engagement with thestylus decomposes at a relatively low temperature in a short time toprovide a clear, sharp mark on the blank, and which decomposes before itmelts permitting the stylus to move at a relatively high velocitywithout sticking.

A further object of the present invention is the provision of a new andimproved recording blank having an indefinite storage life since it ishighly resistant to acidity, humidity, and abrasion and is normallyunaffected by atmospheric conditions.

i Another object of the present invention is to provide a highlysensitive recording blank comprising a base material having a coatingincluding polyvinylidene chloride, wherein the coating is provided witha color t-o contrast with the color of a mark formed on the blank byengaging the coating with a heating stylus which decomposes the coating.A

A further object of the present invention is the provision of a highlysensitive recording blank, as noted in the next preceding paragraph,wherein suitable reagents are includedin the coating to aid in thedecomposition thereof when the coating is engaged by the heating stylus.

A further object of the present invention is the provision of arecording blank, asrnoted in the next preceding paragraph, wherein thereagents may include zinc oxide and preferably zinc chloride, andwherein the zinc chloride dissolves the zinc oxide to provide very smallparticle sizes which greatly facilitate and aid decomposition of thecoating by establishing more intimate physical contact between moleculesof the reagents and the polyvinylidene chloride. Y v

A still further object of the present invention is the provision of anew and improved easily manufactured recording blank comprising a basematerial with a coating of polyvinylidene chloride thereon, wherein thecoating is easily and uniformly applied to the base.

Applicant is aware of prior art attempts to provide `a heat sensitivepaper having Va coating which includes lpolyvinyl chloride. vover apolyvinyl chloride coating. The use of a poly- Applicants coating hasadvantages Vinyl chloride coating providesa blank wherein thetemperature at which a heating sstylus can mark the blank is relativelyhigh when compared to the temperature at which a polyvinylidene chloridecoating, asprovided herein, is marked. Since applicants coatingcontaining t polyvinylidene chloride can be marked at a lowertemperature than known coatings containing polyvinyl chloride, asharper, clearer mark is achieved because the amount of other materialsincluded in the iinal'product which burn is minimized and less sludge isproduced to .interfere with the sylus. Moreover, the marking stylus icecan move faster over applicants polyvinylidene chloride coating sincethe temperature at which a mark is achieved is lower, and also becausethe coating does not soften before it decomposes, in which event thestylus tends to stick or drag. Thus, the stylus is able to move at afaster velocity, and an even sharper line is provided.

Further objects and advantages of the present invention will be apparentto those skilled in the art to which the invention relates from thefollowing detailed description of a preferred embodiment made withreference to the drawings which form a part of this specification, andin which,

FIG. 1 is a perspective view of a recording blank embodying the presentinvention and a stylus adapted to mark the blank; and

FIG. 2 is an enlarged sectional view of the recording blank of FIG. 1taken on the section line 2-2 of FIG. 1.

Referring to the drawings, the present invention is shown as embodied ina recording blank A which is adapted to be mlarked by Ia heating stylusB. The blank A includes a base materical C and a heat sensitive coating12 on the base material and which decomposes or carbonizes to provide amark on the blank when the stylus B engages the coating 12.

The bvase C of the blank is preferably electrically conductive, and inthe illustrated embodiment comprises a strip of aluminum 13 laminated toa strip of paper 14. The base may alternatively, and preferably does,comprise \a zinc plate which aids the decomposition or carboniziation ofthe coating when engaged by a heating stylus, as will be discussedhereinbelow. Many other conventional and well known materials may beutilized for the base of thebl-ank such as paper impregnated withcarbon, metal foils, etc.

The coating 12 includes vinylidene chloride, and may be polyvinylidenechloride alone. Prefenably the coating includes a copolymer ofvinylidene chloridev -and acrylonitrile. Suitable materials formingdecomposing or carbonizing aids or reagents are also prefenably includedin the coating material and are discussed more fully hereinbelow.

The coating 12 is formed of a number of materials which are mixed toform a coating mixture which is applied to the base C. These materialspreferably include a copolymer of vinylidene chloride vwithacrylonitrile, as mentioned above, reagents including preferably zincoxide and Zinc chloride, and a suitable vollatile solvent. Preferably,acetone is used as the solvent but ethyl acetate or methyl ethyl ketonecould also be used as the solvent. Also, suitable additional solventscould be used, such as toluene, propyl alcohol, etc., which control therate of evaponation of the more volatile solvent.

The following table contains the relative quantities of each of thematerials which preferably are included in the coating mixture and thepreferred range of the percentage of each ingredient by weight:

The proportions of the ingredients set forth in the above table :arepreferred land Imay be varied. The amount of solvent can be changed toprovide `la coating of the desired viscosity for easy application, andthe amounts of zinc oxide, zinc chloride, and copolymer of vinylidenechloride with acrylonitrile can be changed to change the Vthey are mixedand dissolves the zinc oxide.

stirred for about two hours at room temperature.

timbres.

contnast between the coating and the mark made by the stylus and tochange the eciency of the marking operation, as will be discussedhereinbelow. However, if the amount of zinc chloride becomes too greatthe shelflife of the coating will be shortened.

The most desirable method ofV making the coating mixture begins withweighing the zinc oxide :and the acetone and pouring them into `amixture vessel. The zinc chloride is then added to the zinc oxide andacetone mixture vwhile the mixture is being stirred. Precaution shouldbe taken to prevent the zinc chloride which is highly deliquescent kfromabsorbing water from the atmosphere, which has a detrimental effect onthe mixture, although a negligible amount of water may be :absorbed bythe Vzinc chloride when adding it to the zinc oxide and lacetone.

The zinc chloride combines with the zinc oxide when The dissolving ofthe zinc oxide by the zinc chloride substantially reduces the size ofthe particles of the zinc oxide. The zinc oxide Iand zinc chloride actas reagents or decomposing aids when the coating is engaged by theheating stylus, and reducing the zinc oxide to an extremely smallparticle size establishes a more intimate physical contact 'between themolecules of the zinc oxide land zinc chlloride ,and of the{polyvinylidene chloride thus greatly enhancing the decomposition orcarbonization of the coating Iand providing the most effective resultswhen the coating is ydecomposed or lcarbonized by the heating stylus.

The zinc chloride, zinc oxide, and acetone are preferably mixed in asuitable mill until a uniform mixture is formed, and the mixture is thenmilled for a suicient length of time to reduce the size of the zincoxide particles which vwere not reduced by the zinc chloride which, asabove Imentioned, enhances the action of these materials to aid thedecomposition or carbonization of the coating. The milling time can varydepending upon the mode of milling and the particle size desired.Milling in a conventional ball mill for twenty-four hours would besufficient.

The copolymer of vinylidene chloride and acrylonitrile is then added tothe mixture and the mixture is then The mixture is placed on the basesheet C to be coated as soon as possible after formation. The coating isapplied in a manner to completely cover the surface of the material,filling all surface recesses and providing a smooth uniform coating inintimate contact with the surface, avoidin-g air Applying the coatingmixture to the base sheet is simplified because the coating mixture issmooth and uniform, free of lumps, and because of the nature of the`solvents used which areeasily absorbed by the base sheet C. The coatingis then dried for an adequate length of time at temperatures under 200F. The drying operavtion evaporates the acetone from the mixture and theare connected to a source of electrical energy and thus anV electricalcurrent is caused to flow through the blank A when the stylus B engagesthe heat sensitive coating 12. This current How heats the coating 12 andcauses it to decompose or carbonize in the area Where the stylus engagesthe coating, which results in a clear, sharp mark on the blank. Otherheating styluses, of course, could be used to provide a mark which donot cause a current to liow through the blank A, but alternatively heatthe coating 12.

' Such heating styluses could be used in the absence of any conductivematerials in the blank A. Y

The decomposing aidsor reagents used in the preferred 1 embodimentfunction when the coating is engaged by the heating stylus to aid in thethermal decomposition of the f fcoating 12. Moreover, if a zinc plate isused as the base material, it also aids in the decomposition of thecoating and thus -greatly enhances the marking of the blank.

Preferably, as above noted, a combination of Zinc chloride and zincoxide are used as reagents. This combination gives the coating a whiteappearance which is Whiter than would be achieved if zinc oxide wereused alone. Since the copolymer of vinylidene chloride is clear incolor, the zinc chloride and zinc oxide comprise a means providing acolor to provide a contrast between a mark formed thereon and thecoating, for without the zinc chloride or zinc oxide or some other meansfor providing a contrast, the coating Would be clear and there would belittle contrast to aid the visual observance of the mark on the blank.Thus a mark on the coating in such asituation would be diiiicult todiscern, whereas a mark on the coating which includes a contrast betweenthe mark and the coating is extremely clear, particularly when thecoating has a white appearance, which highlights the mark formed bydecomposition of the coating. It should be clear that byvarying theamounts of zinc oxide, zinc chloride and polyvinylidene chloride in themixture, the contrast can be varied.

As above noted, the rea-gents including zinc oxide and zinc chlorideprovide the desired contrast, however, this contrast may bev provided byother additives, including pigments, or by the so-called blush effect.As an alternative to the use of zinc oxide, other metal oxide pigmentsmay be used, such as titanium dioxide and which when added to zincchloride are dissolved thereby. Such metal oxide pigments will affectthe decomposing action of the coating somewhat differently than the Zincoxide and to certain extents may be more desirable. For example, thetitanium dioxide when used greatly reduces the corrosive fumes which arecreated by the decomposition of the coating including zinc oxide.

The blush effect, of course, as is Well known, provides a cloudy whiteappearance -on the coating which results from the condensation ofmoisture out of the air into the film and the subsequent cooling of thefilm surface. Normally, of course, this is undesirable but it can beutilized to provide the necessary contrast in the coating of the presentinvention. This blush effect can also be provided by the addition of asmall amount of other solvent less volatile than acetone or the solventused in the mixture that in turn has no ainity with it.V

While the above descrip-tion has discussed the desirability of usingzinc chloride and zinc oxide as reagents, it should be understood, ofcourse, that other decomposing aids or reagents may be used, suoh asiron and copper base materials. Furthermore, rather than using zincchloride along with zinc oxide, other zinc halides might be usedincluding zinc iodide and/or zinc bromide as substituents for the zincchloride.

The coating material formed by the formula set forth in the above tablehas been decomposed in an oven at approximately 212 F. in one minute andat approximately 365 F. in one second. It should be readily apparent,therefore, that a stylus would provide instant marking since a styluswould be capable ofy heating the coating to 212 F. instantly. 'Iheserelatively low temperatures permit the use of stylus or pen velocitiesin` excess of those in the prior art known to applicant, leaving amarkedly visible trace. Also, the coating decomposes before it melts andthus the coating does not melt and does not blur or smear the lineformed by the heating stylus, and thus an extremely sharp and clear markresults. The fact that the temperature at which the coating 'is markedis relatively low results in the heat being limited to the area beneaththe stylus. Moreover, since the pen velocity is relatively high, an even-sharper and clearer mark results. Furthermore, there is no sticking ofthe stylus or pento the coating creating a drag on the stylus. Also, atthe relatively lowrtemperatures the base to which the coating is appliedwill not burn.

Thus it can be seen that the vinylidene chloride coating when engagedlby the stylus B is quickly decomposed and forms a smooth line in thearea where the stylus engages the coating and permits the stylus totravel at a relatively high velocity. The line formed by the stylus issharp and clear when contrasted with the relatively rough and jaggedlines formed on prior art blanks. Also, since the vinylidene chloridecoating is highly resistant to acids, moisture and abrasive action theblank A is of a more permanent nature and has Ia greater storage lifethan the prior art blanks.

While the blank shown in the drawings is of a flat coniiguration itshould be noted thatthe blank could be of any desired configuration ktoconform with the requirements of the machine or .apparatus which isbeing used to mark the blank. For example, a drum or similarconfiguration could be used.

While the preferred embodiment of the presen-t invention has beendescribed in considerable detail hereinabove, it should be understoodthat certain changes and modifications thereof may be made by thoseskilled in the art, and that the invention is not intended to beIlimited to the specific embodiments described, but is intended to coverall changes coming within the scope of the appended claims.

Having described my invention, I claim:

1. A blank for receiving visual intelligence on Iselected areascomprising a base 'material having two planar surface portions, one ofsaid surface portions having a smooth uniform coating dried thereon andsubstantially covering all of said one surface portion and in intimateadhered contact with said'one `surface portion, said coating being anonpowdery cohesive mass of material `decomposable by heating above 212F. and comprising a Y copolymer of vinylidene chloride and acrylonitrileand Zinc oxide and zinc chloride reagent materials which aid in thedecomposition of said copolymer, with the proportion by weight of thereagent material to the copolymer being about 21/2 to 1 and theproportion by Weight of zinc oxide to zinc chloride being about 4 to 1.

2. A blank for receiving visual intelligence on selected areascomprising an electrical current conducting base material having twoplanar surface portions, one of said surface portions having a smoothuniform coating dr-ied thereon and substantially covering said onesurface portion and in intimate -adhered contact with said one surfaceportion, said coating being a nonpowdery cohesive mass of material whichdecomposes and changes in color in the area Where an electricalpotential is applied thereto and comprising a copolymer of vinylidenechloride and acrylonitrile and zinc oxide and zinc chloride reagentmaterials which aid in the decomposition of said copolymer, with theproportion by weight of the reagent l material to the copolymerbeingiabout 21/2 to 1 and the proportion by weight of zinc oxide to zincchloridebeing about 4 to 1.

3. A blank for receiving visual intelligence on selected areascomprising a base material having two planar surface portions, one ofsaid surface portions having a smooth uniform coating dried thereon andsubstantially covering all of said one surface portion and in intimateadhered contact with said one surface portion, said coating being anonpowdery cohesive-mass of material decomposable by heating above 212F. -and comprising a material selected from the group comprisingpolyvinylidene chloride anda copolymer of vinylidene chloride andacrylonitrile and zinc oxide and zinc chloride reagents which aid in thedecomposition of'said materal, with the proporton by Weight of thereagents to said material being within the ratio range of 5/4 to 5/1 andthe proportion by weight of zincroxide to zinc chloride being within theratio range of 8/ 1 to 2/1.

4. The blank receiving visualintelligence on selected areas as definedin claim 3 wherein said base material 5. A blank for receiving visualintelligence on selected i areas comprising a base material having twoplanar surface portions, one of said surface portions having a smoothuniform coating dried thereon and substantially covering all of said one:surface portion and in intimate adhered Contact with said one surfaceportion, said coating being a nonpowdery cohesive mass of materialdecomposable by heat'mg above 212 F. and comprising a material selectedfrom the group comprising polyvinylidene chloride and a copolymer ofvinylidene chloride and acrylonitrile, zinc chloride reagent which aidsin the decomposition of said material, and a metal oxide pigment whichis dissolved when mixed with zinc chloride with the proportion by weightof the reagent and pigment to'said material being within the ratio rangeof 5 4 to 5/ 1 and the proporion by weight of the pigment to the zincchloride being within the ratio range of 8/1 to 2/ 1.

6. A blank for receiving visual intelligence on selected areascomprising a base material having two planar surface portions, one ofsaid surface portions having a smooth uniform coating dried thereon andsubstantially covering all of said one surface portion and in intimateadhered contact with said one surface portion, .said coating being anonpowdery cohesive mass of material decomposable by heating above 212F. and comprising a material selected from the group comprisingpolyvinylidene chloride and a copolymer of vinylidene chloride andacrylonitrile, zinc chloride reagent which aids in the decomposition ofsaid material, and titanium dioxide with the proportion by weight of thezinc chloride and titanium dioxide to said material being within'theratio range of 5/ 4 to 5 l and the proportion by weight of the titaniumdioxide to the zinc chloride being within the ratio range of 8/1 to 2/1.

7. A blank for receiving visual intelligence on selected areascomprising a -base material having two planar surface portions, one ofsaid surface portions having a smooth uniform coating dried thereon andsubstantially covering all of said one surface portion and in intimateadhered contact with said one surface portion, said coating being anonpowdery cohesive mass of material decomposable by heating above 212F. and comprising a materialselected from the group comprisingpolyvinylidene chloride and a copolymer of vinylidene chloride andacrylonitrile and zinc oxide and a zinc halide as reagents which aid inthe decomposition of said r'naterial, with the proportion by weight ofthe reagents to said material being within the ratio range of 5/4 to 5/1and the proportion by weight of zinc oxide to zinc halide being withinthe ratio range 8. A blank for receiving visual intelligence on selectedareas comprising a base material having two planar surface portions, oneof said surface portions having a smooth uniform coating dried thereonand substantially covering all of said one surface portion and inintimate adhered contact with said one surface portion, said coatingbeing a nonpowdery cohesive mass of material decomposable by heatingabove 212 F. and comprising a material selected from the group`comprising polyvinylidene chloride and a copolymer of vinylidenechloride and acrylonitrile, a halide of metal selected from the groupcomprising zinc, iron and copper which aids in the decomposition of saidmaterial and a metal oxide pigment which is dissolved when mixed withthe metal halide.

References Cited by the Examiner 2,855,266 10/1958 James l17-36.8X

WILLIAM D. MARTIN, Primary Examiner. H. W. MYLIUS, Assistant Examiner.

1. A BLANK FOR RECEIVING VISUAL INTELLIGENCE ON SELECTED AREASCOMPRISING A BASE MATERIAL HAVING TWO PLANAR SURFACE PORTIONS, ONE OFSAID SURFACE PORTIONS HAVING A SMOOTH UNIFORM COATING DRIED THEREON ANDSUBSTANTIALLY COVERING ALL OF SAID ONE SURFACE PORTION AND IN INTIMATEADHERED CONTACT WITH SAID ONE SURFACE PORTUON, SAID COATING BEING ANONPOWDERY COHESIVE MASS OF MATERIAL DECOMPOSABLE BY HEATING ABOVE212*F. AND COMPRISING A COPLYMER OF VINYLIDENE CHLORIDE ANDACRYLONITRILE AND ZINC OXIDE AND ZINC CHLORIDE REAGENT MATERIALS WHICHAID IN THE DECOMPOSITION OF SAID COPOLYMER, WITH THE PROPORTION BYWEIGHT OF THE REAGENT MATERIAL TO THE COPLYMER BEING ABOUT 21/2 TO 1 ANDTHE PROPORTION BY WEIGHT OF ZINC OXIDE TO ZINC CHLORIDE BEING ABOUT 4 TO1